Silver halide photographic light-sensitive material

ABSTRACT

A silver halide photographic light-sensitive material is disclosed. The light-sensitive material comprises a support having thereon a silver halide emulsion layer and optionally a hydrophilic colloid layer, at least one of said emulsion layer and said hydrophilic colloid layer contains a water-soluble polymer which comprises repeating unit represented by formula 1 in an amount of 10 to 100 mol %, and a electric conductive layer being provided between the support and the silver halide emulsion layer and comprising a binder and fine particles of an electric conductive crystalline metal oxide of ZnO, Ti0 2 , SnO 2 , Al 2  O 3 , In 2  O 3 , SiO 2 , MgO, BaO, MoO 3 , V 2  O5 or a mixture thereof, each of which has a volumetric resistivity of not higher than 10 7  Ωm; ##STR1## wherein R 1  and R 2  are each independently a hydrogen atom, an alkyl group, a halogen atom or a --CH 2  COOM 1 , in which M 1  is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; L is --CONH--, --NHCO--, --COO--, --OCO--, --SO 2  --, --HSO 2  --, --SO 2  NH-- or --O--; J is an alkylene group, an arylene group or an aralkylene group; Q is a hydrogen atom, --R 3 , ##STR2## in which M 2  is a hydrogen atom or a cation; R 9  is an alkyl group having 1 to 4 carbon atoms; R 3 , R 4 , R 5 , R 6 , R 7  and R 8  are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a phenyl group, an aralkyl group; X is an anion; M is a hydrogen atom or a cation; p and q are each 0 or 1; and Y is a hydrogen atom or a --(L) p  --(J) q  --Q group. The light-sensitive material has a good antistatic property without fogging due to a ultra rapid processing.

FIELD OF THE INVENTION

The present invention relates to a silver halide photosensitivematerial, and more particularly relates to an antistatic silver halidephotosensitive material capable of being very quickly processed.

BACKGROUND OF THE INVENTION

In general, silver halide photographic light-sensitive materialcomprises an insulating plastic film support, on which there areprovided a light-sensitive emulsion layer, antihalation layer,protective layer, intermediate layer, foundation layer and back coatinglayer. Therefore, silver halide light-sensitive material is easilycharged with static electricity. Especially when the temperature is low,for example, in the winter, silver halide light-sensitive material ischarged with static electricity while it is handled, so that problemsmay be encountered. For example, due to the progress of manufacturingtechnique of silver halide photosensitive material, the speed of coatingand that of cutting are increased in the manufacturing process recently.Therefore, frictional electrification occurs. Further, the speed of filmconveyance is remarkably increased in the photographing and processingof films. For this reason, problems are encountered when the films areelectrostatically charged.

When photosensitive material is charged with static electricity, foreignobjects such as dust are deposited on the surface of photosensitivematerial. Therefore, serious problems may occur on a developed image. Inthe case of a medical film, there is a possibility of making a wrongdiagnosis. Further, due to the discharge of accumulated staticelectricity, fog referred to as a static mark is caused, and it becomesimpossible to make a correct diagnosis.

In order to solve the above problems, antistatic agents are applied tosilver halide photosensitive material. For example, a surface activeagent of polyoxyethylene is generally used for the antistatic agent.However, when such a chemical compound is used, there is a possibilitythat streaks of development are caused due to quick processing.According to the method disclosed in Japanese Patent Publication Open toPublic Inspection (JP O.P.I. Publication) No. 142350/1988 in which ahighly soluble surface active agent is used, the surface active agent isdissolved in the processing solution in the process of development andreacts with other substances in the solution, so that trubidness, sludgeand streaks of development are caused.

In order to solve the above problems, Japanese Patent ExaminedPublication Nos. 49894/1985 and 16057/1986 disclose the followingtechnique:

A support is used which has an undercoat layer having antistaticproperties when the undercoat layer contains a metallic oxide. When theabove support is used, even if an amount of the surface active agent ofpolyoxyethylene is reduced or made to be zero, the occurrence of streaksof development can be reduced without deteriorating the effect ofpreventing static marks.

However, even in the above method using a metal oxide, the followingproblem may be encountered:

When the temperature and the value of pH of the developing solution areraised and also an amount of the fog inhibitor is reduced for thepurpose of increasing the processing speed, the occurrence of fog isincreased.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide silver halidelight-sensitive material given a excellent antistatic property withoutincreasing the forming of fog even when the temperature and the value ofpH of a developing solution are high, development processing can becarried out very quickly.

The photographic light-sensitive material of the invention comprises asupport having thereon a silver halide emulsion layer and optionally ahydrophilic colloid layer, at least one of said emulsion layer and saidhydrophilic colloid layer contains a water-soluble polymer whichcomprises repeating unit represented by formula 1 in an amount of 10 to100 mol %, and an electric conductive layer being provided at a positionbetween the support and the silver halide emulsion layer and comprisinga binder and fine particles of an electric conductive crystalline metaloxide of ZnO, TiO₂, SnO₂, Al₂ O₃, In₂ O₃, SiO₂, MgO, BaO, MoO₃, V₂ O₅ ora mixture thereof, each of which has a volumetric resistivity of nothigher than 10⁷ Ωcm; ##STR3## wherein R¹ and R² are each independently ahydrogen atom, an alkyl group, a halogen atom or a --CH₂ COOM¹, in whichM¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; L is--CONH--, --NHCO--, --COO--, --OCO--, --SO₂ --, --HSO₂ --, --SO₂ NH-- or--O--; J is an alkylene group, an arylene group or an aralkylene group;Q is a hydrogen atom, --R³, ##STR4## in which M² is a hydrogen atom or acation; R⁹ is an alkyl group having 1 to 4 carbon atoms; R³, R⁴, R⁵, R⁶,R⁷ and R⁸ are each independently a hydrogen atom, an alkyl group having1 to 20 carbon atoms, an alkenyl group, a phenyl group, an aralkylgroup; X is an anion; M is a hydrogen atom or a cation; p and q are each0 or 1; and Y is a hydrogen atom or a --(L)_(p) --(J)_(q) --Q group.

The light-sensitive material is adapted to a rapid processing in whichwhole processes are carried out within 30 seconds in total.

DETAILED DESCRIPTION OF THE INVENTION

Crystalline metal oxide particles are used for the conductive metaloxide in the present invention. Metal oxide particles containing oxygendefects are preferably used, and also metal oxide particles containing asmall amount of another kind of atoms forming an electron donor withrespect to the used metal oxide are preferably used because the electricconductivity of such metal oxide is generally high. Especially, thelatter is preferably used because the occurrence of fog can be avoidedin a silver halide emulsion.

Usable examples of the metal oxide are: ZnO, TiO₂, SnO₂, Al₂ O₃, In₂ O₃,SiO₂, MgO, BaO, MoO₃ and V₂ O₅, and their mixtures. Especially, ZnO₂,TiO₂ and SnO₂ are preferably used. Effective examples of a case in whichanother kind of atoms are contained, are addition of Al or In to ZnO;addition of Sb, Nb or halogen elements to SnO₂ ; and addition of Nb orTa to TiO₂.

An amount of addition is preferably in a range from 0.01 to 30 mol %,and more preferably in a range from 0.1 to 10 mol %.

The metallic oxide particles usable for the present invention areelectrically conductive, and the volumetric resistivity there of is nothigher than 10⁷ Ωcm, more preferably not lot higher than 10⁵ Ωcm.

The fine particles of the electrically conductive crystalline metaloxide or metal oxide mixture can be prepared by the methods, forexample, described in JP I.O.P. Publication 143430/1981. Concretely,they can easily prepared in the following manner: (1) particles of themetal oxide prepared by baking is subjected to heat treatment in thepresence of another kind of atom which raises electric conductivity ofthe metal oxide powder, (2) particles of the metal oxide is prepared bybaking in the presence of another kind of atom which raises electricconductivity of the metal oxide powder, or (3) at the time of baking themetal oxide to make fine particles thereof, oxygen concentration in theatmosphere is lowered for introducing oxygen vacancies into the metalpowder.

The size of particles is preferably 0.01 to 0.7 μm, and more preferably0.02 to 0.5 μm.

These oxides are described in JP O.P.I. Publication Nos. 143431/1981,120519/1981 and 62647/1983.

The conductive metal oxides usable in the present invention aredispersed in the binder and provided between the support and the silverhalide emulsion layer.

In order to reduce the resistance of the conductive layer by effectivelyutilizing these conductive oxides, it is preferable that the volumetriccontent of the conductive metal oxide particles in the layer is high.However, in order to provide a competent mechanical strength, it isnecessary to add at least 5% of binder. Therefore, the volumetriccontent of the conductive metal oxide is preferably in a range from 5 to95% in value.

It is preferable that the conductive metal oxide is used in an amount of0.05 to 10 g/m², more preferably, 0.1 to 5 g/m², of light-sensitivematerial. Due to the foregoing, a competent antistatic property can beprovided.

In the invention, the conductive layer containing the metal oxideparticles is provided as an under-coat layer at a position between thesupport and the silver halide emulsion layer.

The conductive under-coat layer may be provided in the following manner:

Electrically conductive particles are dispersed in the binder of theunder coat layer, and the under coat layer is directly coated on thesupport. Alternatively, a hydrophilic polymer layer is further coated onit, and an emulsion layer is coated. Usable examples of the binder ofthe under coat layer are a latex polymer, water soluble polymer,cellulose ester, and soluble polyester.

Usable examples of latex polymers are latex of copolymer containingpolyvinyl chloride, copolymer containing vinylidene chloride, glycidylacrylate, copolymer containing glycidyl methacrylate, copolymercontaining alkylester of acrylic acid, and copolymer containingbutadiene. Specifically, the latex is described in JP O.P.I. PublicationNos. 135526/1976, 43911/1975, 114120/1976, 121323/1976 and 112677/1977and Japanese Patent Publication No. 14434/1976.

Examples of the hydrophilic colloid binder usable in the silver halideemulsion layer, hydrophilic colloid layer and the electric conductiveparticles-containing layer include gelatine, gelatine derivative, maleicanhydride copolymer such as vinyl acetate-maleic anhydride copolymer,and cellulose ester such as cellulose acetate, cellulose acetatebutylate and nitrocellulose. Usable examples of soluble polyester arediscloses in JP O.P.I. Publication No. 1612/1979, and Japanese PatentPublication Nos. 2529/1969 and 10432/1960.

A matting agent may be added into the protective layer. Usable examplesof the matting agent are a homopolymer of polymethyl mathacrylatedescribed in U.S. Pat. Nos. 2,992,101, 2,701,254, 4,142,894 and4,396,706; a copolymer of methyl methacrylate and methacrylic acid; andparticles of starch and silica. Further, the surface active agent may beused together.

A lubricant may be added into the surface protective layer. Usableexamples of the lubricant are silicon compounds described in U.S. Pat.Nos. 3,489,576 and 4,047,958, colloidal silica described in JapanesePatent Publication No. 23139/1981, paraffin wax, higher fatty acid esterand starch.

A plasticizer may be added into the hydrophile colloidal layer. Usableexamples of the plasticizer are polyol of trimethylol-propane,pentanediol, butanediol, ethyleneglycol and glycerin.

Usable examples of the support used for the present invention are atransparent or opaque synthetic resin film of polyethyleneterephthalate, cellulose acetate, polycarbonate, polystyrene andpolypropylene and a paper support laminated with polyethylene resin.

The thickness of the support is preferably 50 to 200 μm, and morepreferably 100 to 180 μm.

Various types of additives for example, described on pages 22 through 28of Vol. 176432 of Research Disclosure (RD) published in December of1978, may be added to the above emulsion layer or hydrophilic colloidallayers.

The method of coating these emulsion layer and hydrophilic colloidallayers is also disclosed in Research Disclosure described above.

In the invention, a water-soluble polymer is added into at least one anemulsion layer or a hydrophilic colloid layer such as a surfaceprotective layer, back-coating layer, intermediate layer, under-coatinglayer and anti-halation layer other than the layer in which theconductive metal oxide particles are added to make it to a electricconductive layer.

Water soluble polymers usable in the present invention will be explainedas follows.

Water solube polymers usable in the invention preferably have asolubility in water of about 0.05 g or more per 100 g of water at thetemperature of 20° C. More preferably, the solubility is not less than0.1 g per 100 g of water at 20° C. It is preferable that the watersoluble polymers each has a high solubility with respect to thedeveloping and fixing solutions. The preferable solubility of the watersoluble polymer, is not less than 0.05 g per 100 g of the developingsolution. The solubility in the developing solution is, more preferably,not less than 0.5 g, and further preferably, not less than 1 g, per 100g of the developing solution.

Natural or synthetic water soluble polymers may be used. Synthetic watersoluble polymers may be used in the invention may have nonionic groups,anionic groups, or both nonionic and anionic groups in the molecularstructure. In this case, examples of the nonionic group are an ethergroup, ethylene oxide group, and hydroxy group. Examples of the anionicgroup are a sulfonic acid group or its salt, carboxylic acid group orits salt, and phosphoric acid group and its salt.

A homopolymer or copolymer may be used as the synthetic water solublepolymer. As long as the polymer itself is water-soluble, the copolymerpartially derived from a hydrophobic monomer may be used.

In some cases, the composition of the copolymer is restricted by aposition where it is added and an amount of copolymer to be added. Forexample, when the copolymer is added to an emulsion layer and the amountof which is large, the composition of the copolymer is determined sothat the effect of addition is not deteriorated.

Natural water soluble polymers usable in the invention may have nonionicgroups, anionic groups, or both nonionic and anionic groups in themolecular structure.

Preferable water soluble polymers in the invention are ones containing arepeating unit represented by the following formula 1. Especially, thefollowing repeating unit may be contained in the polymer by 10 to 100mol %. ##STR5##

In the formula, R¹ and R² each independently a hydrogen atom, an alkylgroup, a halogen atom, or --CH₂ COOM¹, M¹ is a hydrogen atom or an alkylgroup having 1 to 8 carbon atoms. In the above, the alkyl group ispreferably one having 1 to 4 carbon atoms which may have a substituent,for example, a substituted or unsubstituted methyl, ethyl, propyl orbuthyl group.

L represents --CONH--, --NHCO--, --COO, --OCO, --CO--, --SO₂ --, --NHSO₂--, --SO₂ NH-- or --O--.

J is an alkylene group, prepeferably an alkylene group having 1 to 10carbon atoms, including one having a substituent such as a substitutedor unsubstituted methylen, ethylene, propylene, trimethylene, butylene,and hexylene group; an arylene group including substituted one such as asubstituted and unsubstituted phenylene group; or a substituted orunsubstituted aralkylene group such as ##STR6## .paren open-st.CH₂ CH₂O.paren close-st._(m) .paren open-st.CH₂ .paren close-st._(n) or .parenopen-st.CH₂ CHCH₂ O.paren close-st._(m) .paren open-st.CH₂ .parenclose-st._(n), wherein m is an integer from 0 to 40, and n is an integerfrom 0 to 4. Q is a hydrogen atom, --R³, ##STR7##

In the above, M is a hydrogen atom or a cation group; R⁹ is an alkylgroup having 1 to 4 carbon atoms such as a methyl, ethyl, propyl orbutyl group; R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are each independently analkyl group having 1 to 20 carbon atoms such as a substituted orunsubstituted methyl, ethyl, propyl, butyl, hexyl, decyl or hexadecylgroup, an alkenyl group such as a substituted or unsubstituted vinyl orallyl group, a phenyl group such as a phenyl, methoxyphenyl,chlorophenyl group or those each further having a substituent; anaralkyl group such as a substituted or unsubstituted benzyl group; X isan anion; and p and q are each 0 or 1. A polymer containing acrylamideor methacryl amide is particularly preferable.

Y represents a hydrogen atom or --(L--)p--(J--)q--Q.

The repeating unit represented by formula 1 may be copolymerized withethylenic unsaturated monomer to from the synthetic water solublepolymer. Usable examples of copolymerizable ethylenic monomer includesstyrene; alkylstyrene and hydroxylalkylstyrene in which the alkyl grouppreferably has 1 to 4 carbon atoms, for example, methyl, ethyl and butylare preferably; vinylbenzenesulfonic acid and its slat; α-methylstyrene; 4-vinylpiridine; N-vinylpyrolidone; monoethylenic unsaturatedester of fatty acid such as, vinylacetate and vinylpropionate; ethylenicunsaturated monocarboxylic or dicarboxylic acid and its salt, forexample, acrylic acid and methacrylic acid; maleic acid anhydride;ethylenic unsaturated monocarboxylic acid or ester of dicarboxylic acid,for example, n-butyl acrylate, N, N-diethylaminoethyl mathacrylate; andan amide of ethylenic unsaturated monocarboxylic acid or carboxylicacid, for example, acrylamide, 2-acrylamide-2-methylpropane sulfonate,N, N-dimethyl-N'-methacryloylpropanediamine acetate betaine.

Next, examples of the specific chemical compound of the syntheticwater-soluble polymer having the repeating unit shown in the generalformula 1 will be described below. The values written in parentheses arenumber average molecular weights Mn. ##STR8## Wherein, n₁ :n₂ =50 mol %:50 mol %, and the number average molecular weight (Mn)=about 10,000.##STR9## Wherein, n₁ :n₂ =75 mol %:25 mol %, and Mn=about 20,000.##STR10##

When the above synthetic water soluble polymers are used, the molecularweight is preferably 1,000 to 100,000, and more preferably 2,000 to50,000.

Examples of usable natural water soluble polymers are described in"Technical Data of Water Soluble Polymer and Water Dispersion Resin",1981, published by Business Development Center Publishing Department.Usable examples of the natural water soluble polymers are lignin,starch, pullulan, cellulose, alginic acid, dextran, dextrin, guar gum,gum arabic, pectin, casein, agar, xanthan gum, cyclodextrin, locust beangum, tragacanth gum, carrageenan, glycogen, laminaran, lichenin,nigeran, and their derivatives.

Preferable derivatives of the natural water soluble polymers includeones each having a sulfo group, a carboxyl group, a phosphoric acid andits salt group, a sulfoalkyl group, carboxylalkylene group, analkylphsphoric group and its salt, an polyoxalkylene group such aspolyoxyethylene, polyoxyglyceline, polyoxypropylene group and an alkylgroup such as methyl, ethyl and benzyl group.

Concerning the natural water soluble polymers, two or more kinds of themmay be used together.

Concerning the natural water soluble polymers, a glucose copolymer andits derivatives are preferably used. Especially, starch, glycogen,cellulose, lichenin, dextran and nigeran are preferably used. Dextranand its derivatives are more preferably used.

Dextran is a polymer of D-glucose of α- 1,6 bond. In general, dextran isobtained when dextran producing bacteria are cultured in the presence ofsugars. When dextran sucrase separated from the culture medium ofdextran producing bacteria such as leuconostoc and mesenteriodes isreacted with sugars, dextran can be obtained. When the obtained nativedextran is subjected to the partially decomposing polymerization inwhich acid or alkali enzyme is used, the molecular weight is lowered toa predetermined value, so that the dextran of which the limitingviscosity number is in a range from 0.03 to 2.5 can be provided.

Examples of modified dextran are dextran sulfate, carboxyalkyldextran,and hydroxialkyldextran. The molecular weight of the natural watersoluble polymer is preferably 100 to 100,000, and more preferably 2,000to 50,000.

Producing methods of dextran and its derivatives are described inJapanese Patent Publication Nos. 11989/1960, 12820/1970, 18418/1970,40149/1970, 31192/1971 and U.S. Pat. No. 3,762,924.

In the present invention, an adding amount of synthetic or natural thewater soluble polymer is preferably 0.01 to 3.0 g/m², and morepreferably 0.05 to 1.0 g/m².

Silver halide photosensitive material according to the invention can beapplied for any types of photographic material such as medialradioactive ray radigraphic material, laser beam recording photographicmaterial, directly positive type photographic material, photographicmaterial for graphic arts, color negative photographic material,reversal color photographic material, color photographic paper thermaldevelopment photographic material, and diffusion transfer typephotographic material.

Silver halide emulsion usable in the silver halide photographic materialof the present invention includes silver chloride, silver bromide,silver chlorobromide, silver iodobromide and silver chloroiodobromideemulsions having arbitrary halide composition. However, from theviewpoint of high sensitivity, silver bromide or silver iodobromidehaving an average content of silver iodide of 0 to 5.0 mol, andpreferably 0.1 to 3.0 mol, is preferably used.

In silver halide emulsion, the composition of halide may be uniform inthe particles, or silver iodide may be partially localized. It ispreferable that silver iodide is locatized at the center portion of thesilver halide grain.

Methods of producing silver halide emulsion are described in JP O.P.I.Nos. 113926/1983, 113927/1984, 113934/1983 and 1855/1987, and EuropeanPatent Nos. 219,849 and 219,850. For preparing monodispersed tabularsilver halide emulsion, JP O.P.I. No. 6643/1986 can be referred.

A tabular silver iodobromide emulsion having a high aspect ratio can beprepared by the followings. An aqueous solution of silver nitrate oraqueous solution of silver nitrate and that of halide are simultaneouslyadded to an aqueous gelatine solution, maintaining the pBr value to benot more than 2, to form seed crystals. Then the seed crystals are madeto grow by the double jet method.

Various photographic additives may be added to the silver halideemulsion applied to the invention, at a time during physical ripening orbefore and after chemical ripening. Examples of well known additives aredescribed in Research Disclosure (RD), the volumes of which are No.17643 (published in December of 1978), No. 18716 (published in Novemberof 1979) and No. 308119 (published in December of 1989). Types of thesecompounds and pages of Research Disclosure on which these compounds aredescribed are as follows.

    __________________________________________________________________________            RD-17643 RD-18716  RD-308119                                                      Classifi- Classifi-  Classifi-                                    Additive                                                                              Page                                                                              cation                                                                             Page cation                                                                             Page  cation                                       __________________________________________________________________________    Chemical                                                                              23  III  648  Upper                                                                              996   III                                          sensitizer            right                                                   Spectral                                                                              23  IV   648-649   996-998                                                                             IVA                                          sensitizer                                                                    Desensitizing                                                                         23  IV             998   IVB                                          dye                                                                           Dye     25-26                                                                             VIII 649-650   1003  VIII                                         Development                                                                           29  XXI  648  Upper                                                   accelerator           right                                                   Antifogging                                                                           24  IV   649  Upper                                                                              1006-1007                                                                           VI                                           agent                 right                                                   Whitening                                                                             24  V    998  V                                                       agent                                                                         Hardening                                                                             26  X    651  Left 1004-1005                                                                           X                                            agent                                                                         Surface active                                                                        26-27                                                                             XI   650  Right                                                                              1005-1006                                                                           XI                                           agent                                                                         Antistatic                                                                            27  XII  650  Right                                                                              1006-1007                                                                           VIII                                         agent                                                                         Plasticizer                                                                           27  VII  650  Right                                                                              1006  XII                                          Lubricant                                                                             27  VII                                                               Matting agent                                                                         28  XVI  650  Right                                                                              1008-1009                                                                           XVI                                          Binder  26  XXII           1003-1004                                                                           IV                                           __________________________________________________________________________

Supports usable for the photosensitive material of the present inventionare described on page 28 in Vol. 17643 and on page 647 in Vol. 18716 ofResearch Disclosure.

A polyethylene terephthalate film is appropriately used for the support.A subbing layer is preferably provided on the surface of the support,and also it is preferable that the surface of the support is subjectedto corona discharge or ultraviolet ray irradiation so that the coatinglayers can be appropriately adhered on the surface.

Photographic processing of the photographic material of the invention ispreferably carried out in 30 seconds that is a period of time from whena fore end of the photosensitive material to be processed enters a filminsertion sensor of the automatic developing apparatus to when the foreend of the photosensitive material reaches a discharge sensor of theautomatic developing apparatus. In the developing apparatus, forexample, processing may be carried out by the .processing solutiondescribed on pages 29 to 30 of XX to XXI of the above RD-17643, or pages1011 to 1012 of XX to XXI of the above RD-308119. This photographicprocessing may be a monochromatic processing. The processing temperatureis commonly in a range from 18° C. to 50° C.

In the monochromatic photographic processing, the following developingagents are used alone or in combination: hydroxybenzene (for example,hydroquinone), 3-pyrazolidone (for example, 1-phenyl-3-pyrazolidone),and aminophenol (for example, N-methyl-p-aminophenol). In thisconnection, well known preservatives, an alkaline agent, pH buffer,antifogging agent, development accelerator, surface active agent,antifoaming agent, color toning agent, water sofener, dissolutionassistant, and thickener, may be used in the developer according tonecessity.

Tiosulfate or tiocyanate is used for the fixing agent. Water solublealuminum salt such as aluminum sulfate or potash alum may be containedas a hardening agent. Preservatives, pH adjusting agent and watersofener may be contained.

EXAMPLE Example 1

Preparation of supports A and B

A 175 μn thick polyethylene terephthalate film, which was tinted to beblue with a density of 0.15, was subbed on both side with the followingcomposition, so that the support (A) was prepared.

    ______________________________________                                        Gelatine       30 mg/m.sup.2                                                  Salicylic acid 15 mg/m.sup.2                                                  ______________________________________                                    

Reacted product of polyamide composed of diethylenetriamine and amidineacid with epichlorohydrin 30 mg/m².

A conductive under coat layer of the following composition was coated onboth sides of the above subbed support (A), so that the support (B) wasprepared. SnO₂ /Sb used in support (B) had a volumetric resistivity of3.5 Ω·cm.

Further support (C) was prepared in the same manner as in support (B)except that SnO₂ /Sb was replaced by ZnO₂ /Al particle having an averagesized of 0.6 μm, ZnO₂ /Al ratio in mol of 9/1 and a volumetricresistivity of 3×10² Ω·cm.

    ______________________________________                                        Gelatine                30 mg/m.sup.2                                         SnO.sub.2 /Sb (the mol ratio is 8/2, and the average                                                  300 mg/m.sup.2                                        particle size is 0.25 μm)                                                  C.sub.9 H.sub.19 --C.sub.6 H.sub.4 --O(CH.sub.2 CH.sub.2 O).sub.8                                      3 mg/m.sup.2                                         ______________________________________                                    

Preparation of emulsion Em-1

Preparation of seed emulsion.

A hexagonal tabular seed emulsion was prepared by the following method.

    ______________________________________                                        (Solution A)                                                                  Ossein gelatine          60.2   g                                             Distilled water          20.0   l                                             Sodium salt of polyisopropyleneoxy-                                                                    5.6    ml                                            polyethyleneoxy-dicuccinate                                                   KBr                      26.8   g                                             10% H.sub.2 SO.sub.4     144    ml                                            (Solution B)             3500   ml                                            2.5N AgNO.sub.3 aqueous solution                                              (Solution C)                                                                  KBr                      1029   g                                             KI                       29.3   g                                             ______________________________________                                    

Distilled water is added so that the total amount is made to be 3500 ml.

    ______________________________________                                        (Solution D)                                                                  ______________________________________                                        1.75N KBr water solution                                                                         an amount necessary to                                                        maintain the silver                                                           electrode potential at the                                                    following value                                            ______________________________________                                    

At a temperature of 35° C., using the mixing and stirring apparatusdescribed in Japanese Patent Nos. 58288/1983 and 58289/1983, 64.1 ml ofsolution B and also 64.1 ml of solution C were added to 64.1 ml ofsolution A by a double-jet mixing method spending 2 minutes so as toform nucleuses.

After the stop of addition of solutions B and C, the temperature ofsolution A was raised to 60° C. spending 60 minutes. Then solutions Band C were added by a double-jet mixing method at a flow rate of 68.5ml/min for 5 minutes. During this operation, the silver electrodepotential of the emulsion was controlled to be +6 mV using solution D,wherein the silver electrode potential was measured by the silver ionselecting electrode while a saturated silver-silver chloride electrodewas used as a comparative electrode.

After the addition, the pH value was adjusted to be 6 by 3% KOH, andimmediately desalting and washing were carried out so that seed emulsionEm-0 was obtained. The seed emulsion Em-0 was inspected with an electronmicroscope and it was confirmed that 90% or more of the total projectedarea of the silver halide particles was composed of hexagonal tabularparticles, the adjacent edge ratio of which was 1.0 to 2.0. The averagethickness of the hexagonal tabular particles was 0.07 μm, and theaverage diameter, which is a value converted to the diameter of acircle, was 0.5 μm.

Tabular silver iodide emulsion EM-1 was prepared using the following 4solutions.

    ______________________________________                                        Solution E                                                                    Ossein gelatine     29.4 g                                                    Seed emulsion Em-0 Amount corresponding to                                                       1.6 mol of silver                                          Sodium salt of polyypropyreneoxy-                                                                  2.5 ml                                                   polyethyreneoxy-disuccinate                                                   Distilled water to make 1400 ml.                                              Solution F         2360 ml                                                    3.5N AgNO.sub.3 water solution                                                Solution G                                                                    KBr                 963 g                                                     KI                  27.4 g                                                    Distilled water to make 2360 ml.                                              Solution H                                                                    1.75N KBr          an amount necessary to                                                        maintain silver electrode                                                     potential at the following                                                    value                                                      ______________________________________                                    

At the temperature of 60° C., using the mixing and stirring apparatusdescribed in Japanese Patent Nos. 58288/1983 and 58289/1983, and theoverall amounts of solutions F and G were added to solution A by thedouble jet method at the flow rate of 21.26 ml/min spending 111 minutesso as to form nucleuses. During this operation, the silver electrodepotential was controlled to be +25 mV using solution H. Next, in orderto remove an excessive amount of salt, precipitation demineralizationwas conducted using a water solution of Demol N (manufactured by KaoAtlas CO.) and a solution of magnesium sulfate, and an aqueous solutionof 92.2 g of ossein gelatin was added so that the total amount was madeto be 2500 ml and stirred and dispersed. Thus Em-1 was obtained.

The grains of Em-1 were tabular silver iodide in which the diameter ofan average projected area was 0.65 μm, the particle thickness was 0.26μm, the aspect ratio was 2.5, and the silver iodide content was 1.1mol%.

Preparation of Em-2

Highly monodispersed cubic silver iodobromide grains were used as seedgrains, which had an average grain size of 0.2 μm, an iodide content of2.0 mol % and a grain size variation coefficient indicationmonodispersed degree of 0.15. The seed grains were grown withiodobromide having a iodide content of 30 mol % at pH of 9.8 and pAg of7.8. To thus obtained emulsion, equimoles of potassium bromide andsilver nitrate were added at pH of 8.2 and pAg of 7.8 to prepareemulsion Em-2 composed of monodispersed tetradeca-hedral silveriodobromide grains having an average iodide content of 2.2 mol %,average grains size of 0.54 μm and a grain size variation coefficient of0.17.

The emulsion was desalted by the common floculation sedimentation so asto remove an excessive amount of salt. While the temperature wasmaintained at 40° C., Demol N, condensated products of formalin andnaphthalene sodium sulfonate, and a aqueous solution of magnesiumsulfate were added to the emulsion so as to be coagulated, andsupernatant liquid was removed.

Distilled water was added to each of obtained silver halide emulsionsEm-1 and Em-2 so that the volume was 300 ml per 1 mol of silver. Thenthe temperature was raised to 55° C., and the spectral sensitizers (A)and (B) described later were added by a total amount of 540 mg in thecase of Em-1 and 400 mg in the case of Em-2. The weight ratio of (A) and(B) was 10:1.

After 10 minutes had passed, ammonium tiocyanate was added by an amountof 2×10⁻³ mol and 4×10⁻³ mol with respect to 1 mol of silver to Em-1 andEm-2, respectively. Further, appropriate amounts of chloroauric acid andsodium thiosalfate were added to each emulsions to start chemicalripening. The ripening was carried out at pH of 6.5 and silver electrodepotential of 50 mV.

With respect to Em-1, fine particles of silver iodide were added by anamount of 4.0 g per 1 mol of silver 70 minutes before the completion ofchemical ripening. Further, 4-hydroxy-6-methyl-1,3,3a,7-tetrazinden wasadded in an amount of 3×10⁻² mol for stabilization. With respect toEm-2, potassium iodide was added in an amount of 200 mg per 1 mol ofsilver 15 minutes before the completion of chemical ripening (70 minutesafter the start of chemical ripening). Then, 10% (wt/vol) acetic acidwas added 5 minutes after, so that the value of pH was lowered to 5.6,and that value of pH was maintained for 5 minutes. Then, a 0.5% (wt/vol)solution of potassium hydroxide was added so that the value of pH wasreturned to 6.15. After that, 4-hydroxy-6-methyl-1,3,3a,7-tetrazindenwas added in an amount of 3×10⁻² mol for stabilization.

After the preparation of the emulsion coating solution, the value of pHwas adjusted to be 6.20 and the silver electrode potential was adjustedto 80 mV at 35° C. using a solution of sodium carbonate and a solutionof potassium bromide.

Using the emulsion coating solution described above, samples wereprepared in the following manner. The photographic emulsion layer wasprovided on both side of the support so that the emulsion amount couldbe 2.0 g/m² per one side in terms of silver. An amount of gelatine andthat of polymer latex per one side were adjusted to be the values shownon Table 1.

Protective layer solution was prepared using the additives describedlater. The protective layer solution was prepared so that the amount ofgelatine and the added amount of polymer latex per one side could be thesame as the values described on Table 1. Therefore, together with theemulsion coating solution, the protective layer solution wassimultaneously coated on both sides of the support at the speed of 80m/min using two sets of slide hopper coaters. The coated layers weredried for 2 minutes and 20 seconds. In this way, the samples wereobtained. In this case, the supports A and B were used.

The following spectral sensitizers were used for the preparation ofsamples.

Spectral sensitizer (A)

Anhydride sodium salt of5,5'-di-chloro-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine

Spectral sensitizer (B)

Anhydride sodium salt of5,5'-di-(butoxycarbonyl)-1,1'-diethyl-3,3'-(4-sulfobutyl)-bezimidazolocarbocyanine

The following additives were used for the emulsion coating solution.

An amount of addition is shown by an amount per 1 mol of silver halide

    ______________________________________                                        1,1-dimethylol-1-bromine-nitromethane                                                                  10       mg                                          t-Butyl catechol         70       mg                                          Styrene-maleic anhydride copolymer                                                                     2.0      g                                           Nitrophenyl-triphenyl phosphonium chloride                                                             5.0      mg                                          Ammonium 1,3-dihydroxybenzene-4-sulfonate                                                              2.0      g                                           Sodium 2-mercaptobenzimidazole-5-sulfonate                                                             1.5      g                                           C.sub.4 H.sub.9 OCH.sub.2 CH(OH)CH.sub.2 N(CH.sub.2 COOH).sub.2                                        1.5      G                                           1-phenyl-5-mercaptotetrazole                                                                           15       mg                                          Water-soluble polymer given in Table 1                                                                 Refer Table 1                                         ##STR11##               150      mg                                           ##STR12##               70       mg                                          trimethylolpropane       10       g                                            ##STR13##               500      mg                                           ##STR14##               100      mg                                          ______________________________________                                    

Next, additives used for the protective layer solution are shown asfollows. Weight shows a value contained in 1 litter of coating solution.

    ______________________________________                                        Lime-processed inert gelatine                                                                             58     g                                          Acid-processed gelatine     2      g                                          Sodium i-aluminum-n-decylsulfone succinate                                                                1.0    g                                          Polymethyl methacrylate                                                       Matting agent, silicon dioxide particle having an area                                                    0.4    mg                                         average particle size is 1.2 μm                                            Ludox AM (colloidal silica manufactured by                                                                3.0    g                                          Dupon Co.)                                                                    2,4-dichloro-6-hydroxy-1,3,5-triazine sodium                                                              10     ml                                         salt 2% aqueous solution                                                      Glyoxal 40% aqueous solution (hardening agent)                                                            5.0    ml                                         (CH.sub.2CHSO.sub.2 CH.sub.2).sub.2 O (hardening agent)                                                   36     mg                                          ##STR15##                  0.25   g                                          C.sub.12 H.sub.25 CONH(CH.sub.2 CH.sub.2 O).sub.5 H                                                       3.0    g                                          ______________________________________                                    

Dye emulsifying dispersion liquid was prepared as follows. The followingdyes were respectively measured so that the amount was 10 kg. Then thedyes were dissolved in a solvent containing 28 litters of tricresylphosphate and 85 litters of ethyl acetate at 55° C., which is referredto as an oily solution. On the other hand, anion surface active agentand 1.35 kg of the following (AS) were dissolved at 45° C., and 270millilitters of 9.3% gelatine aqueous solution was prepared, which isreferred to as a aqueous solution.

The aforementioned oily and aqueous solutions were put in a dispersionkettle and dispersed while the temperature was controlled to be 40° C.

To the thus obtained dispersion substance, 8 g of the following additiveC and 16 litters of water solution of phenol 2.5% and water were addedso that the total amount was adjusted to be 240 kg. Then, it was cooledand gelled. ##STR16##

The area average particle sizes of the thus obtained dispersionsubstance were in a range from 0.12 to 0.14 μm. The above coatingsolution was uniformly coated on both surfaces of the blue polyethyleneterephthalate supports (A) and (B) provided with the above under coatlayer. Then the coating solution was dried. In this way, the samples 1to 10 were made as shown on Table 1. With respect to all samples, anamount of coated gelatine was adjusted so that the amount could be 3.0g/m² on both surface. An amount of coated silver on each sample wasadjusted to be 2.0 g/m² on one side.

Sensitometry Test

The obtained samples were exposed to white light in the followingmanner:

Standard light source B described on page 39 of the second print of thefirst edition of "New Edition Illumination Data Book" published by theSociety of Illumination was used for the light source. The sample wasexposed for 0.1 second at 3.2 CMS with no filter. In this whiteexposure, both sides of a film were exposed so that amounts of exposurelight could be the same on both sides. The exposed samples weresubjected to development processing by the following method.

The following processing conditions were adopted.

A remodeled automatic processor SRX-502 (manufactured by Konica Co.) wasused. A developer and a fixer of the following compositions were used.The developing temperature was 37° C., and the fixing temperature was33° C. The washing was carried out at 18° C. by supplying water of 7.0litters per minute. The drying temperature was 55° C. All processes wereperformed in the following 30 and 45 second modes. The results on Table1 represent the relative sensitivity in the case where the sensitivityof No. 1 sample was set at 100.

    ______________________________________                                                 Processing    Processing                                                                              Replenishing                                 Process  temperature (°C.)                                                                    tie (sec) amount                                       ______________________________________                                        30 Second Processing Mode                                                     [Process]                                                                     Insertion                                                                              --            0.8                                                    Development                                                                            37            9.7       270 ml/m.sup.2                               Fixing   33            5.5       430 ml/m.sup.2                               Washing  18            4.8        7.0 l/m.sup.2                               Squeeze  45            3.8                                                    Drying   55            5.4                                                    Total    --            30.0                                                   45 Second Processing Mode                                                     [Process]                                                                     Insertion                                                                              --            1.2                                                    Development                                                                            37            14.6      270 ml/m.sup.2                               Fixing   33            8.2       430 ml/m.sup.2                               Washing  18            7.2        7.0 l/m.sup.2                               Squeeze  40            5.7                                                    Drying   40            8.1                                                    Total    --            45.0                                                   ______________________________________                                    

In the above, the times of development fixing and washing each includesthe time necessary to transporting the sample from a processing tank tothe next processing tank.

    ______________________________________                                        Developer                                                                     Part-A (for use in 15 litter finish)                                          Potassium hydroxide        470    g                                           Potassium sulfite (50% solution)                                                                         3000   g                                           Sodium bicarbonate         150    g                                           Diethylene triamine penta-acetic acid,                                                                   45     g                                           penta-sodium salt                                                             5-methylbenztriazole       2.0    g                                           1-phenyl-5-mercaptotetrazole                                                                             0.2    g                                           Hydroquinone               390    g                                           Water to make 5000 ml                                                         Part-B (for use in 15 litter finish)                                          Glacial acetic acid        220    g                                           Triethylene glycol         200    g                                           1-phenyl-3-pyrazolidone    27     g                                           5-nitroindazolol           0.45   g                                           n-acetyl-D,L-penicillamine 0.15   g                                           Water to make 5000 ml                                                         Starter (for use in 1.0 litter finish)                                        Glacial acetic acid        138    g                                           Potassium bromide          325    g                                           5-methylbenztriazole       1.5    g                                           CH.sub.3 N(C.sub.3 H.sub.6 NHCONHC.sub.2 H.sub.4 SC.sub.2 H.sub.5).sub.2                                 20     mg                                          Water to make 1.0 l                                                           To the developer 20 cc/l of starter was added.                                Fixer                                                                         Part-A (for use in finishing 19 litters)                                      Ammonium thiosulfate (70 wt/vol %)                                                                       4000   g                                           Sodium sulfite             175    g                                           Sodium acetate trihydrate  400    g                                           Sodium citrate             50     g                                           Gluconic acid              38     g                                           Boric acid                 30     g                                           Glacial acetic acid        140    g                                           Part-B (for use in finishing 19 litters)                                      Aluminum sulfate (in term of anhydrous salt)                                                             65     g                                           Sulfuric acid (50 wt %)    105    g                                           ______________________________________                                    

Measurement of antistatic property

The antistatic property was investigated in the following manner:

Humidity of an unexposed sample was adjusted at 23° C. under thecondition of relative humidity 20% for 2 hours. After that, in a darkroom maintained under the same air condition, the sample was rubbed by arubber or nylon roller. The the sample was subjected to the sameprocessing as described above.

The occurrence of static marks was visually evaluated. The reference ofevaluation is described as follows.

A: Static marks do not occur.

B: Static marks occur in an area lower 3%.

C: Static marks occur in an area not less than 3% and lower than 10%.

D: Static marks occur in an area not less than 10%.

The results are shown on Table 1.

                                      TABLE 1                                     __________________________________________________________________________                 Water soluble                                                                 polymer                                                                              Amount of                                                                           Processing                                          Sample                                                                            Used                                                                              Used        addition                                                                            time  Relative Static                               No. support                                                                           emulsion                                                                           Exemplified                                                                          (g/m.sup.2)                                                                         (sec) sensitivity                                                                         Fog                                                                              marks                                                                             Remark                           __________________________________________________________________________    1   A   Em-1 --     --    30    100   0.03                                                                             D   Comparative                                                                   example                          2   B   Em-1 --     --    30    100   0.03                                                                             A   Comparative                                                                   example                          3   A   Em-1 I-2    0.2   30     98   0.03                                                                             D   Comparative                                                                   example                          4   B   Em-1 I-2    0.04  30    100   0.03                                                                             A   Present                                                                       invention                        5   B   Em-1 I-2    0.2   30     98   0.03                                                                             A   Present                                                                       invention                        6   B   Em-1 I-2    1.0   30     98   0.03                                                                             A   Present                                                                       invention                        7   B   Em-1 I-17   0.5   30    100   0.03                                                                             A   Present                                                                       invention                        8   B   Em-1 I-5    0.2   30    100   0.03                                                                             A   Present                                                                       invention                        9   B   Em-2 I-7    0.5   30     96   0.03                                                                             A   Present                                                                       invention                        10  B   Em-2 I-23   0.5   30     98   0.03                                                                             A   Present                                                                       invention                        11  A   Em-1 --     --    45    105   0.05                                                                             D   Comparative                                                                   example                          12  B   Em-1 --     --    45    105   0.08                                                                             A   Comparative                                                                   example                          13  A   Em-2 I-2    0.5   45     98   0.03                                                                             D   Comparative                                                                   example                          14  B   Em-2 I-2    0.5   45     98   0.05                                                                             A   Present                                                                       invention                        15  B   Em-2 I-5    0.5   45     99   0.05                                                                             A   Present                                                                       invention                        16  C   Em-2 I-2    0.5   45     98   0.05                                                                             A   Present                                                                       invention                        __________________________________________________________________________

As can be seen from Table 1, even after the total processing (Dry toDry) of 30 seconds, the sensitivity of the sample of the presentinvention was not deteriorated, and the occurrence of fog was low, andthe sample of the present invention was excellent in the anti-staticmark property.

What is claimed is:
 1. A silver halide photographic light-sensitivematerial comprising a support having thereona silver halide emulsionlayer, and optionally a hydrophilic colloid layer, at least one of saidlayers containing a water-soluble polymer, and an electric conductivelayer being provided between said support and said silver halideemulsion layer and comprising a binder and fine particles of an electricconductive crystalline metal oxide selected from the group consisting ofZnO, TiO₂, SnO₂, Al₂ O₃, In₂ O₃, SiO₂, MgO, BaO, MoO₃, V₂ O₅ and amixture thereof, each of which has a volumetric resistivity of nothigher than 10⁷ Ωcm; and wherein said water-soluble polymer is selectedfrom the group consisting of ##STR17## wherein, n₁ :n₂ =50 mol %: 50 mol%, and the number average molecular weight (Mn)=about 10,000, ##STR18##wherein, n₁ :n₂ =75 mol %: 25 mol %, and Mn=about 20,000, ##STR19##wherein in the above, the values written in parentheses are numberaverage molecular weight.